Dyestuff of the anthraquinone series and process of making same



Patented Feb. 9, 1932 UNITED "STA S GEORG KALISCHER, or rRAnKFoar-on-rHn-Mmm AND EnNsr rronorro, or FRANK- PATENT OFFICE FORT-ON-THE-MAIN-FEOHENHEIM, GERMANY, AE IGNORSfTOQGENERAL ANILINE WORKS, INC., OF NEW YORK, N. Y., A. CORPORATION OF DELAWARE nYEsrUrr or rnn-nnrrmneumonn sER rEs Ann rnocnss or" MAKING SAME No Drawing. Application filed January 29, 1929, Serial No. 336,001, and in Germany February 1 1928.

a Our present invention relates to new acid wool dyestuffs of the anthraquinone series and consists in condensing an l-aminolhalogeno-anthraquinone-2-sulfonic acid of the general formula O ITIH:

SOaH

wherein R has the above signification.

The condensation is advantageously carried out in an'aqueous' or alcoholic solution. The mercaptansmay be applied in .the form of their alkali or heavy metal salts, e. g. of the Zinc salts; A11 addition of catalyst is scarcely necessary for our process as the.re

action runs very smoothly and quickly. In order to obtain'dyestufi's containing sulfonic M groups attached to the arylor aralkyl residue;

the l-amino-L-arylor -aralkyl-mercaptoanthraquinone-Q-sulfonic'acids may be subjected toa subsequent sulfonating process.

The dyestuffs obtained according to our process by starting from the special 1-amino -halogeno-anthraquinone-2-sulfonic acids are new, they are soluble in water, dye wool from an acid bath red toviolet shades of an excellent fastness and possess a peculiarly good levelling property compared with the known wool dyestufis of the anthraquinone stated therein.

Ewample 1 V A solution of parts of the sodium salt of 1 amino 4 -bro1no anthraquinone-Q-sulfonic acid and 19 parts of the sodium salt of 4- chloro-l-mercapto-benzene in 400 parts of water is boiled in an apparatus provided with a reflux condenser. The lightred solution becomes dark red after a short time.

When the reaction is finished the dyestuff is isolated by addition of common salt. It represents a dark red powder and corresponds probably to the formula:

It dyes wool from an acid bath very fast strong bluish red" shades and dissolves in sulfuric acid to a light orange-red solution formaldehyde. When l-chloro-1-mercapto-benzene is returning to green when mixed with para"- shade and nearly equal properties are obtained'in like manner.

Example 2 I-amino-d-bromo -anthraquinone-fl-sulfonic acid is condensed with 4-chloro-2.5-dimethyl-lemercapto-benzene as describedin Ex- Ill) ample 1. The dyestuff thus produced sponds probably to the formula:

It dissolves in sulfuric acid to a brownish red solution and dyes wool fast reddish violet shades.

Example 3 1-amino-4r br0mo-anthraquinone-2-sulfonic acid is condensed with l-methyl-l-mercap to-benzene as described in Example 1. The dyestuff thus produced corresponds probably to the formula:

0 NHz FSOaH i i w A LOOHS It dyes wool reddish violet shades of an eX- cellent fastness and possesses an especially good levelling property.

The dyestuff may be sulfonated by being treated at with live times its amount of sulfuric acid monohydrate. This product is easily soluble and dyes wool a shade not essentially different from that of the starting dyestufi'.

Example 4 80 parts of the sodium salt of l-amino-tbromo-anthraquinone-2-sulfonic acid and parts of the sodium salt of 9-mercapto-anthracene are dissolved in 1000 parts of water and the solution is boiled for a short time. The new dyestufl already separates partially from the hot solution in a crystalline form. The precipitation is completed by addition of common salt. The dyestufl thus isolated represents a red powder and corresponds probably to the formula:

0 NHz It dissolves in concentrated sulfuric acid to a yellowish orange solution and dyes wool from an acid bath dark reddish Violet shades.

By treating this dyestulf at a moderate temperature with concentrated sulfuric acid,

a higher sulfonated product is obtained which shows a similar shade and a higher solubility.

E xample 5 A solution of 20 parts of the sodium salt of l-aminol -brom0 anthraquinone 2 sulfonic acid and 7 parts of sodium benzylmercaptide in 1000 parts of water is boiled for 20-30 minutes. The solution is filtered and mixed with common salt. The dyestuf'f thus isolated corresponds probably to the formula:

lO NHz SOaH It dyes wool dark reddish violet shades and posseses a good fastness and levelling property.

Example 6 dissolves in concentrated sulfuric acid to an orange solution and dyes wool reddish brown shades. I

When instead of Q-amino-5-eth0Xy-benzene-l-mercaptide the corresponding amount of 2-amino-3-methyl-5-chloro-benzene-1-mercaptide is used, adyestufli' dyeing wool claret shades is produced.

We claim:

1. A process which comprises condensing an l-amino-4l-halogeno-anthraquinone-2-sulfonic acid of the general formula:

SOaH

y) lal with ,a mercaptan of the general formula I-ISR, wherein R means an aryl or aralkyl group.

2. A process which comprises condenslng 1 amino 4 bromo anthraquinone -2-su1fonic acid. of the formula:

o Nm 7 son:

' with 4c-methyl-l-mercapto-benzene of the formula 3. As new compounds Wool dyestufl' of the anthraquinone series corresponding prob ablyto the general formula:

wherein R means an aryl or aralkyl group.

4:. As a new compound a wool dyestufi of the anthraquinone series corresponding probably to the formula:

SOaH

t In testimony whereof, we aifix our signaures.

GEORG KALISCHER. ERNST HONOLD. 

